This invention generally relates to organic resins, more particularly to resins having an internal structure comprised of polyamide and polyether, and terminal structure comprised of hydrocarbon. The invention also relates to the preparation of these resins, and their use as, for example, gelling agents for organic solvents.
In many commercially important compositions, the consistency of the product is critical to its commercial success. One example is personal care products, which generally contain one or more active ingredients within a carrier formulation. While the active ingredient(s) determine the ultimate performance properties of the product, the carrier formulation is equally critical to the commercial success of the product in that it largely determines the consistency of the product. The rheology of the carrier (also referred to as the xe2x80x9cbasexe2x80x9d) largely determines the flow properties of the product, and the flow properties largely determine the manner in which the consumer will apply or use the product.
For example, aluminum chlorohydrate, aluminum-zirconium tetrachlorohydrate, aluminum-zirconium polychlorohydrate complexed with glycine, and aluminum-zirconium complexed with any of trichlorohydrate, octachlorohydrate, and sesquichlorohydrate are metal salts that are commonly used as active ingredients in deodorant and antiperspirant products. Consumers have shown a preference for applying deodorant from a stick form. Thus, the carrier in a stick-form deodorant must be a relatively hard substance, and waxy fatty alcohol such as stearyl alcohol has often been used as the carrier in these products. As another example, the active ingredient in a lipstick is the colorant. A lipstick should not be as hard as a stick deodorant, but of course must maintain its shape when undisturbed at room temperature. A blend of wax and oil is known to provide a consistency that is well suited as a carrier for a lipstick. As a final example, shampoo desirably has a viscosity greater than water, and when the active ingredient(s) in a shampoo does not have a sufficiently high viscosity, a somewhat viscous carrier material is desirably included in the shampoo formulation.
From the above examples, it is seen that formulators of personal care products depend upon the availability of materials having various rheological properties, in order to formulate a successful personal care product. Materials which have a gel-like character, in that they maintain their shape when undisturbed but flow upon being rubbed, are often desired for personal care products.
Transparent (i.e., clear) carriers are desired by formulators who develop a personal care product wherein colorant is an active ingredient, because a transparent carrier (as opposed to an opaque carrier) will minimally, if at all, interfere with the appearance of the colorant. In recent years, consumers have demonstrated an increasing preference for transparent and colorless personal care products such as deodorants and shampoos. There is thus an increasing demand for transparent materials that can provide the rheological properties needed for various personal care products, and particularly which can impart gel-like character to a formulation.
Polyamide resin prepared from polymerized fatty acid and diamine is reported to function as a gellant in formulations developed for personal care products. For example, U.S. Pat. No. 3,148,125 is directed to a clear lipstick carrier composition formed from polyamide resin compounded with a lower aliphatic alcohol and a so-called xe2x80x9cpolyamide solvent.xe2x80x9d Likewise, U.S. Pat. No. 5,500,209 is directed to forming a gel or stick deodorant, where the composition contains polyamide gelling agent and a solvent system including monohydric or polyhydric alcohols. Thus, the prior art recognizes to blend certain polyamides with alcohols, to thereby form a gel.
Polar solvents, e.g., ether- and hydroxyl-containing materials which are liquid at or slightly above room temperature, are desirably included in personal care formulations because they are often benign, allow dilution with at least some water, dissolve a wide range of active and inactive formulation ingredients and are relatively inexpensive. Polar solvents are also available in a wide variety of viscosities and grades. However, these solvents typically do not have the rheological properties that are desired in a carrier, e.g., they do not naturally exhibit gel-like character. Furthermore, gelants for this type of solvent are uncommon and often unavailable.
Accordingly, there is a need in the art for materials that can be combined with solvents, and particularly polar solvents, to afford a transparent material that has gel-like character. The present invention provides this and related advantages as described herein.
In one aspect, the present invention provides a block copolymer of the formula: hydrocarbon-polyether-polyamide-polyether-hydrocarbon. The present invention also provides compositions that include this block copolymer, where such compositions may also include one or more of a diacid, diamine or hydrocarbon-terminated polyether.
In various aspects: the polyamide block includes blocks of the formula 
where R3 is a hydrocarbon diradical, preferably dimer acid-derived, e.g., wherein the R3 group includes a diradical that results when two carboxylic acid groups are removed from dimer acid; R4 is selected from a hydrocarbon and a polyether diradical; the polyether block includes blocks of the formula "Parenopenst"R2xe2x80x94O"Parenclosest", where R2 is a hydrocarbon; C1-22 hydrocarbon radicals are located at either end of the copolymer, where the hydrocarbon radical may optionally be selected from alkyl, aralkyl, aryl, and alkaryl radicals.
In other aspects, the copolymer has the formula 
independently at each occurrence, R1 is selected from C1-22 hydrocarbon radicals; R2 is selected from C2-6 hydrocarbon diradicals; R3 is selected from C2-52 hydrocarbon diradicals, where at least 50% of the R3 diradicals have at least 34 carbons; R4 is selected from C2-36 hydrocarbon diradicals and C4-C100 polyether diradicals; Z is selected from O and NH; x is an integer from 2 to 100; y is an integer from 1 to 10; Z is NH; R2 is a C2 hydrocarbon diradical; and at least 80% of the R3 diradicals have at least 34 carbon atoms.
In various aspects, the present invention provides a composition that includes a copolymer as described above, that meets one or more of the following criteria: an acid number of less than 25; an amine number of less than 5; a softening point of 50-150xc2x0 C.; a weight average molecular weight of 2,000 to 20,000; a melting point above 50xc2x0 C. and a viscosity at 160xc2x0 C. of less than 5,000 cps.
In another aspect, the present invention provides a process of preparing a block copolymer where the process includes reacting together reactants that include dimer acid, diamine, and a polyether having both hydrocarbon termination and termination selected from one of amine, hydroxyl and carboxyl. The polyether may have the formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94W where R1 is selected from C1-C22 hydrocarbyl, R2 is selected from C2-C6 hydrocarbyl, x is an integer presenting the number of repeating ether units, and W is selected from amine, hydroxyl and carboxyl. The present invention also includes a copolymer and composition prepared by this process.
In another aspect, the present invention provides a gelled composition that includes a hydrocarbon-terminated block copolymer as described above, and a polar organic solvent, the solvent having hydroxyl and/or ether functionality. In a related aspect, the present invention provides a method for preparing a gel, where the method includes combining a hydrocarbon-terminated block copolymer as described above, at elevated temperature with a liquid having hydroxyl and/or ether functionality to provide a mixture, and allowing the mixture to cool to room temperature to form the gel.
In a further aspect, the present invention provides a microemulsion that includes a hydrocarbon-terminated block copolymer as described above, a polar organic solvent, and water.
These and related aspects of the present invention are described more fully herein.
In one aspect, the present invention provides a hydrocarbon-terminated block copolymer of the formula (1)
hydrocarbon-polyether-polyamide-polyether-hydrocarbon. (1)
In formula (1), a hydrocarbon group contains only carbon and hydrogen atoms. Suitable hydrocarbon groups are formed from one or more of aliphatic and aromatic moieties. Suitable aliphatic moieties are alkyl, alkylene, alkenyl, alkenylene, alkynyl, alkylnylene, cycloalkyl, cycloalkylene, cycloalkenyl, cycloalkenylene, cycloalkynyl, and cycloalkynylene moieties. Aromatic moieties are also referred to herein as aryl groups. The hydrocarbon group will be referred to herein as R1.
As used herein, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and cycloalkynyl are monovalent radicals, while alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, and cycloalkynylene are polyvalent radicals. As used herein alkyl, alkylene, cycloalkyl, and cycloalkylene are saturated radicals, while alkenyl, alkenylene, alkynyl, alkylnylene, cycloalkenyl, cycloalkenylene, cycloalkynyl, and cycloalkynylene are unsaturated radicals. The alkyl, alkylene, alkenyl, alkenylene, alkynyl, and alkylnylene moieties may be straight chain or branched. The cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkylene, cycloalkenylene and cycloalkynylene moieties may be monocyclic or polycyclic, where a polycyclic moiety may be, for example, bicyclic or tricyclic.
Exemplary alkyl moieties are methyl, ethyl, propyl, hexyl, and 2-ethylhexyl. Exemplary alkylene moieties are methylene (xe2x80x94CH2xe2x80x94), methylidene (xe2x95x90CH2), ethylene (xe2x80x94CH2CH2xe2x80x94). Exemplary cycloalkyl groups are cyclohexyl and norbornyl.
Suitable aromatic moieties are monocyclic or polycyclic. An exemplary monocyclic aryl group is phenyl, while exemplary polycyclic aryl groups are naphthyl and filverenyl. The aromatic moiety may be monovalent, e.g., phenyl, or polyvalent, e.g., phenylene.
The hydrocarbon group may be a combination of aromatic and aliphatic groups. For example, benzyl (phenyl-CH2xe2x80x94, an arylalkylene group), tolyl (CH3-phenylene-, an alkylarylene group), and xylyl ((CH3)2phenylene-, a dialkylarylene group). The hydrocarbon group may be a combination of two or more aromatic groups, e.g., biphenyl (phenyl-phenylene-, an arylarylene group).
The R1 group necessarily contains at least one carbon. In one embodiment, the R1 group contains 1-32 carbons. In one embodiment, the R1 alkyl group contains 1-12 carbons. In one embodiment, the R1 group is an alkyl group. In one embodiment, the R1 alkyl group is straight-chained. In one embodiment, the R1 alkyl group is branched.
The block copolymer of formula (1) contains at least two polyether blocks. As its name implies, a polyether block contains a plurality of ether groups, i.e., groups of the formula xe2x80x94Cxe2x80x94Oxe2x80x94Cxe2x80x94. In other words, a polyether block contains the repeating formula xe2x80x94Oxe2x80x94R2 xe2x80x94 where R2 is a hydrocarbon group. In one aspect, R2 is an alkylene group. The alkylene group R2 may be aliphatic (saturated and/or unsaturated) or aromatic, straight chain and/or branched, independently at each occurrence in the polyether block. In one aspect, R2 has 1-6 carbons at each occurrence in the polyether block, while in another aspect R2 has 2-4 carbons at each occurrence. In one aspect, R2 has the formula xe2x80x94CH2xe2x80x94CH(R2a)xe2x80x94 wherein R2a is selected from hydrogen, methyl and ethyl.
In one aspect, the polyether component of the block copolymer has a molecular weight (number or weight average) of less than 10,000. In another aspect, the molecular weight is between 100 and 4,000.
The block copolymer of formula (1) contains a polyamide block. As its name implies, the polyamide block contains a plurality of amide groups, i.e., groups of the formula xe2x80x94NHxe2x80x94C(xe2x95x90O)xe2x80x94 and/or xe2x80x94C(xe2x95x90O)xe2x80x94NHxe2x80x94. In the polyamide block, two or more amide groups are separated by hydrocarbon groups, e.g., alkylene groups and/or polyether groups.
In one aspect, the polyamide block contains xe2x80x94C(xe2x95x90O)xe2x80x94R3xe2x80x94C(xe2x95x90O)xe2x80x94 moieties wherein R3 is a hydrocarbon group. In one aspect, the polyamide block includes R3 groups having at least 30 carbons. In one aspect, the polyamide block includes R3 groups having 30-42 carbons.
In one aspect, the polyamide block includes R3 groups that are the formed from fatty acid polymerization. Fatty acids derived from vegetable oils, tallow, and tall oil (the latter are known as tall oil fatty acids, or TOFA) are commercially subjected to thermal polymerization, typically in the presence of a clay catalyst, to provide a product known commercially as dimer acid. These fatty acids contain 18 carbons, so that corresponding dimer acid consists mainly of C36 dicarboxylic acids. This dimer acid may be denoted by the structure HOOCxe2x80x94C34xe2x80x94COOH, where the C34 group is an exemplary R3 group of the present invention. C34 is a mixture of isomeric structures, as more fully described in detailed descriptions of dimer acid, as found in, for example, Naval Storesxe2x80x94Production, Chemistry and Utilization, D. F. Zinkel and J. Russel (eds.), Pulp. Chem. Assoc. Inc., 1989, Chapter 23.
Suitable polymerized fatty acids are available commercially as, for example, SYLVADYM(trademark) dimer acid and UNIDYME(trademark) dimer acid, both from Arizona Chemical, company of International Paper, (Jacksonville, Fla.), EMPOL(trademark) dimer acid from Henkel Corporation, Emery Oleochemicals Division (Cincinnati, Ohio); and PRIPOL(trademark) dimer acid from Unichema North America (Chicago, Ill.).
Dimer acid, as commercially available, typically contains some by-products of the fatty acid polymerization process. One common byproduct is so-called trimer acid, which results when three fatty acid molecules reaact together to form a C64 tricarboxylic acid. It may happen, in the preparation of a block copolymer of the present invention, that two of the carboxylic acid groups of trimer acid will react with, e.g., a diamine, leaving one carboxylic acid group unreacted. When this occurs, the block copolymer will contain a carboxylic acid-substituted R3 group, which is technically not a hydrocarbon. Accordingly, while block copolymers of the present invention contain hydrocarbon groups between two NHC(xe2x95x90O) groups, they may also contain some, typically a minor amount, of carboxylic acid-substituted hydrocarbon groups between two NHC(xe2x95x90O) groups. For convenience, as used herein, C34 refers to the incorporation of dimer acid into a polyamide block, where C34 includes the reaction product of some trimer acid that may be a by-product in the commercial dimer acid.
In one aspect, the present invention provides block copolymers of formula (1) wherein each of the C(xe2x95x90O) groups is bonded to C34, i.e., the block copolymer is formed from dimer acid as the exclusive polyacid reactant. However, in another aspect, the polyamide block includes both C34 and xe2x80x9cco-diacidxe2x80x9d-derived R3 groups. Thus, the polyamide block may be formed by reacting both dimer acid and co-diacid with a diamine.
As used herein, a co-diacid is a compound of formula HOOCxe2x80x94R3xe2x80x94COOH where R3 is not C34 as defined above. In one aspect, the polyamide block in copolymers of formula (1) includes R3 groups having 2-32 carbons, which are referred to herein a co-diacid R3 groups. Suitable co-diacid R3 groups include ethylene (from, e.g., succinic acid) and n-butylene (from, e.g., adipic acid).
In one aspect, the C34R3 groups constitute at least 50 mol % of the total of the R3 groups. In other aspects, the C34R3 groups constitute at least 60 mol %, or 70 mol %, or 80 mol %, or 90 mol %, or 95 mol % of the R3 groups. Stated another way, dimer acid contributes at least 50% of the diacid equivalents, or at least 60-%, or 70%, or 80%, or 90%, or 95% of the diacid equivalents in the polyamide block of the copolymer of formula (1).
In one aspect, the polyamide block contains xe2x80x94NHxe2x80x94R4xe2x80x94NHxe2x80x94 moieties wherein R4 is a hydrocarbon group. In one aspect, the R4 hydrocarbon groups has 1-20 carbons. In one aspect, the polyamide block includes R4 groups having 1-10 carbons. In one aspect, the R4 group is an alkylene group. In one aspect, R4 is a straight-chained alkylene group. In one aspect, the polyamide block includes R4 groups having 2 carbons, while in another aspect at least 50% of the R4 groups have 2 carbons, while in another aspect all of the R4 groups have 2 carbons.
In one aspect, the polyamide block contains xe2x80x94NHxe2x80x94R4xe2x80x94NHxe2x80x94 moieties wherein R4 is a polyether group. As defined above, a polyether block contains a plurality of ether groups, i.e., groups of the formula xe2x80x94Cxe2x80x94Oxe2x80x94Cxe2x80x94. In other words, a polyether block contains the repeating formula xe2x80x94Oxe2x80x94R2xe2x80x94 where R2 is a hydrocarbon group. In one aspect, R2 is an alkylene group. The alkylene group R2 may be aliphatic (saturated and/or unsaturated) or aromatic, straight chain and/or branched, independently at each occurrence in the polyether block. In one aspect, R2 has 1-6 carbons at each occurrence in the polyether block, while in another aspect R2 has 2-4 carbons at each occurrence. In one aspect, R2 has the formula xe2x80x94CH2xe2x80x94CH(R2a)xe2x80x94 wherein R2a is selected from hydrogen, methyl and ethyl.
In one aspect, the polyether component of the R4 potion of the block copolymer of the present invention has a molecular weight (number or weight average) of less than 10,000. In another aspect, the molecular weight is between 100 and 4,000.
Compounds of the formula H2Nxe2x80x94R4xe2x80x94NH2 are commonly known as diamines, and are available from a large number of vendors. Compounds of the formula HOOCxe2x80x94R3xe2x80x94COOH are commonly known as diacids, or dibasic acids, and are likewise available from a large number of vendors. Aldrich (Milwaukee, Wis.; www.sigma-aldrich.com); EM Industries, Inc. (Hawthorne, N.Y.; http://www.emscience.com); Lancaster Synthesis, Inc. (Windham, N.H.; http://www.lancaster.co.uk) are three representative vendors.
In formula (1), the bond xe2x80x98xe2x80x94xe2x80x99 between hydrocarbon and polyether represents a Cxe2x80x94O bond where the carbon is contributed by the hydrocarbon and the oxygen is contributed by the polyether.
In formula (1), in one aspect, the bond between polyether and polyamide is Cxe2x80x94NHxe2x80x94C(xe2x95x90O)xe2x80x94C where Cxe2x80x94NH may be seen as being contributed by the polyether and C(xe2x95x90O)xe2x80x94C may be seen as being contributed by the terminal acid group of a polyamide. Block copolymers according to this aspect may be formed by, for example, reacting an amino and hydrocarbon terminated polyether of the formula R1xe2x80x94(Oxe2x80x94R2xe2x80x94)NH2 with a carboxylic acid terminated polyamide of the formula HOOCxe2x80x94NHxe2x80x94R4xe2x80x94NH- etc. so as to form R1xe2x80x94(Oxe2x80x94R2xe2x80x94)Nxe2x80x94C(xe2x95x90O)xe2x80x94R4. Thus, an amide group may be present as the link between polyether and polyamide in formula (1).
In formula (1), in one aspect, the bond between polyether and polyamide is Cxe2x80x94C(xe2x95x90O)xe2x80x94NHxe2x80x94C where Cxe2x80x94C(xe2x95x90O) may be seen as being contributed by the polyether and NHxe2x80x94C may be seen as being contributed by the terminal amine group of a polyamide. Block copolymers according to this aspect may be formed by, for example, reacting a carboxylic acid and hydrocarbon terminated polyether of the formula R1xe2x80x94(Oxe2x80x94R2xe2x80x94)COOH with an amine terminated polyamide of the formula H2Nxe2x80x94R4xe2x80x94NHxe2x80x94C(xe2x95x90O)xe2x80x94R3-etc. so as to form R1xe2x80x94(Oxe2x80x94R2xe2x80x94)xe2x80x94C(xe2x95x90O)xe2x80x94NHxe2x80x94R4xe2x80x94NHxe2x80x94C(xe2x95x90O)xe2x80x94R3-etc. Thus, once again, an amide group may be present as the link between polyether and polyamide in formula (1).
In formula (1), in one aspect, the bond between polyether and polyamide is Cxe2x80x94Oxe2x80x94C(xe2x95x90O)xe2x80x94C where Cxe2x80x94O may be seen as being contributed by the polyether and C(xe2x95x90O) may be seen as being contributed by the terminal acid group of a polyamide. Block copolymers according to this aspect may be formed by, for example, reacting a hydroxyl and hydrocarbon terminated polyether of the formula R1xe2x80x94(Oxe2x80x94R2xe2x80x94)OH with a carboxylic acid terminated polyamide of the formula HOOCxe2x80x94NHxe2x80x94R4xe2x80x94NH-etc. so as to form R1xe2x80x94(Oxe2x80x94R2xe2x80x94)Oxe2x80x94C(xe2x95x90O)xe2x80x94R4. Thus, an ester group may be present as the link between polyether and polyamide in formula (1).
In one aspect, the present invention provides a composition comprising a hydrocarbon-terminated polyether-polyamide block copolymer of the present invention having an acid number of less than 25, or less than 20, or less than 15, or less than 10. The hydrocarbon-terminated polyether-polyamide block copolymer of formula (1) does not have any free carboxylic acid groups, and accordingly has an acid number of zero. However, when prepared from diacid, diamine and hydrocarbon-terminated polyether according to a process described herein, some of the diacid may not react with the diamine and/or polyether, and according the final product may have some unreacted carboxylic acid that will be responsible for the product having an acid number greater than zero. Preferably, the product has a minor amount of this unreacted diacid, and thus has only a small acid number. Esterification catalysts may be used to encourage all of the diacid to react with hydroxyl groups, so as to minimize the amount of free acid, i.e., to reduce the acid number of the product.
In one aspect, the present invention provides a composition comprising a hydrocarbon-terminated polyether-polyamide block copolymer of the present invention having an amine number of less than 25, or less than 20, or less than 15, or less than 10, or less than 5 or less than 2 or less than 1. The hydrocarbon-terminated polyether-polyamide block copolymer of formula (1) does not have any free amine groups, and accordingly has an amine number of zero. However, when prepared from diacid, diamine and hydrocarbon-terminated polyether according to a process described herein, some of the diamine may not react with the diacid, and according the final product may have some unreacted amine groups that will be responsible for the product having an amine number greater than zero. Preferably, the product has a minor amount of this unreacted diamine, and thus has only a small amine number. Amidification catalysts may be used to encourage all of the diamine to react with carboxyl groups, so as to minimize the amount of free amine, i.e., to reduce the amine number of the product.
In one aspect, the present invention provides hydrocarbon-terminated polyether-polyamide block copolymers, and compositions containing these copolymers, that has a softening point of 50-150xc2x0 C. (Ring and Ball, or Mettler). In another aspect, the softening point is 75-125xc2x0 C., while in another aspect the softening point is 75-100xc2x0 C., while in another aspect the softening point is 80-120xc2x0 C.
In one aspect, the present invention provides hydrocarbon-terminated polyether-polyamide block copolymers, and compositions containing these copolymers, that has a weight or number average molecular weight of 2,000 to 30,000. The molecular weight is measured by preparing a solution of the copolymer or composition in a suitable solvent, e.g., tetrahydrofuran (THF) and identifying the retention time of the copolymer by gel permeation chromatography, and comparing that retention time to the retention times of solutions of polystyrene having known molecular weight characterizations. In one aspect, the copolymers have a weight or number average molecular weight of greater than 1,000. Among other features, the hydrocarbon termination on the polyether reactant allows for control of the molecular weight of the copolymer. If both ends of the polyether reactant were reactive, e.g., the polyether contained hydroxyl functionality at both ends, then the polyether could not be utilized as a terminator in the preparation of copolymers of the present invention.
In one aspect, the present invention provides hydrocarbon-terminated polyether-polyamide block copolymers, and compositions containing these copolymers, that have a viscosity, as measured on the neat copolymer or composition at 160xc2x0 C., of less than 5,000 centipoise (cPs, or cps), or less than 4,000 cPs, or less than 3,000 cPs, or less than 2,000 cPs, or less than 1,000 cPs Typically, the copolymer and compositions will have a melt viscosity, as measured on the neat copolymer or composition at 160xc2x0 C., of more than 50 cPs, typically more than 500 cPs.
Block copolymers of the present invention may be prepared by reacting together compounds of the formulae R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94W, HOOCxe2x80x94R3xe2x80x94COOH, and H2Nxe2x80x94R4xe2x80x94NH2, where W represents either an amine, hydroxyl or carboxylic acid group. As used herein an amine group (xe2x80x94NH2), a carboxylic acid group (xe2x80x94COOH) and a hydroxyl group (xe2x80x94OH) include reactive equivalents thereof. For instance, HOOCxe2x80x94R3xe2x80x94COOH includes reactive equivalents, such as monoesters and diesters, i.e., compounds wherein a carboxylic acid is in esterified form.
Compounds of the formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94W wherein W is hydroxyl are also known as ether-terminated polyalkylene glycols. These compounds are generally well known and may be readily prepared by methodology described in the scientific and patent literature. For example, a monohydric initiator, i.e., a compound of the formula R1xe2x80x94OH is reacted with an alkylene oxide (an R2 group that includes an epoxide group), e.g., ethylene oxide, propylene oxide, etc. to provide a compound of the formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94OH. These compounds are available from, e.g. Aldrich Chemical (Milwaukee, Wis.).
In one aspect, block copolymers are prepared from compounds of formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94W wherein W is hydroxyl and R2 is ethylene (xe2x80x94CH2CH2xe2x80x94). Such compounds of formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94W may be referred to herein as ethoxylates or alcohol ethoxylates. Ethoxylates may be obtained from many commercial sources (e.g., Dow, Midland Mich.) or may be prepared by reacting alcohols of formula R1xe2x80x94OH with ethylene oxide to give the structure (2) below
R1xe2x80x94Oxe2x80x94(CH2CH2O)xxe2x80x94Hxe2x80x83xe2x80x83(2)
where R1 is a hydrocarbon group as defined previously, and in one aspect is a C6-22 alkyl or aralkyl group. Ethoxylates are typically colorless liquids to low melting point pasty solids depending on the chain length (m). Exemplary ethoxylates having various combinations of R1 groups and molecular weight are given in TABLE A (TABLE Axe2x80x94TYPICAL ETHOXYLATES AND THEIR PROPERTIES). In TABLE A, Manuf. is an abbreviation for manufacturer, EO is an abbreviation for ethylene oxide, %EO refers to the weight percent ethylene oxide in the product, EO/OH refers to the molar ratio of ethylene oxide to hydroxyl, HLB refers to the hydrophile lipophile balance, Shell refers to the Shell Chemical division of the Royal Dutch/Shell Group of Companies (www.shell.com) where Shell sells alcohol ethoxylates under the NEODOL(trademark) trademark. Also in TABLE B, Condea refers to CONDEA Vista Company (Houston, Tex.; www.condea.de) which sells a number of alcohol ethoxylates under their brandnames NONFIX(trademark), BIODAC(trademark), LORODAC(trademark), LIALET(trademark), EMULDAC(trademark) and ALFONIC(trademark) where these materials differ by the R1 group, and the number of ethylene oxide groups in the product.
In another aspect, block copolymers are prepared from compounds of formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94W wherein W is hydroxyl and R2 is one or both of ethylene (xe2x80x94CH2CH2xe2x80x94), propylene (xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94), and n-butylene (xe2x80x94CH2CH2CH2CH2xe2x80x94). Such compounds of formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94W may be referred to herein as polyalkyl glycols. Polyalkyl glycols may be obtained from many commercial sources (e.g., Dow, Midland Mich.; Union Carbide, Danbury, Conn.; Aldrich, Milwaukee, Wis.) or may be prepared by reacting alcohols of formula R1xe2x80x94OH with ethylene oxide and/or propylene oxide to give the structure (3) below.
R1xe2x80x94[O(CH2CH2O)x(CH2CH(CH3)O)Y]Hxe2x80x83xe2x80x83(3)
As commercially available, R1 is commonly methyl or n-butyl, but R1 can be any hydrocarbon group. Some typical properties of these materials which are available from Union Carbide and Dow are given in TABLE B (TABLE Bxe2x80x94TYPICAL GLYCOLS AND THEIR PROPERTIES). These materials are also available as the copolymers of ethylene and propylene glycol. In TABLE B, MPEG stands for methyl ether poly(ethylene glycol) (i.e., the repeating unit is always ethylene so that Y=0) MBPPG stands for monobutyl ether poly(propylene glycol) (i.e., the repeating unit is always propylene so that X=0), and MBPEGCPG stands for monobutyl ether poly(ethylene glycol-co-propylene glycol), 50/50 PPG/PPE (i.e., the repeating unit is selected from ethylene and propylene, so that X and Y are each equal to or greater than 1).
In another aspect, block copolymers are prepared from hydrocarbon-terminated polyethers of the formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94W wherein W is carboxylic acid, which are also known as oxa acids. These compounds are generally well known and may be readily prepared by methodology described in the scientific and patent literature. For example, a monohydric initiator, i.e., a compound of the formula R1xe2x80x94OH is reacted with an alkylene oxide (an R2 group that includes an epoxide group), e.g., ethylene oxide, propylene oxide, etc. to provide a compound of the formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94OH. This ether-terminated polyalkylene glycol is the subjected to oxidation conditions to convert the terminal hydroxyl group to a carboxylic acid group. Oxa acids have the structure (4) below:
R1xe2x80x94Oxe2x80x94(CH2CH2O)xxe2x80x94CH2xe2x80x94COOHxe2x80x83xe2x80x83(4).
Compounds of formula (4) where m=1 and 2 are available from Hoechst (now Aventis), as experimental products. Some properties of these acids are give in TABLE C (TABLE Cxe2x80x94TYPICAL OXA ACIDS AND THEIR PROPERTIES). In TABLE C, AN stands for acid number.
In another aspect, block copolymers are prepared from compounds of formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94W wherein W is amine and R2 is one or more of ethylene (xe2x80x94CH2CH2xe2x80x94), propylene (xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94), and n-butylene (xe2x80x94CH2xe2x80x94CH(CH2CH2)xe2x80x94). Such compounds of formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94W may be referred to herein as polyoxyalkyleneamines. These compounds are generally well known and may be readily prepared by methodology described in the scientific and patent literature. For example, a monohydric initiator, i.e., a compound of the formula R1xe2x80x94OH is reacted with an alkylene oxide (an R2 group that includes an epoxide group), e.g., ethylene oxide, propylene oxide, etc. to provide a compound of the formula R1xe2x80x94(Oxe2x80x94R2)xxe2x80x94OH. This ether-terminated polyalkylene glycol is the subjected to reaction conditions to convert the terminal hydroxyl group to a terminal amino group.
Generally, polyoxyalkyleneamines (also known as poly(oxyalkylene) monoamines) have the structure (5) below
R1xe2x80x94OCH2CH2Oxe2x80x94(CH2CHRxe2x80x2O)xxe2x80x94CH2CH(Rxe2x80x3)NH2xe2x80x83xe2x80x83(5)
where R is preferably an alkyl group; Rxe2x80x2 is preferably H, CH3, or C2H5; and Rxe2x80x3 is preferably H or CH3. Commonly available polyoxyalkyleneamines are typically prepared from ethylene oxide and/or propylene oxide and are available commercially in varying ratios of propylene oxide to ethylene oxide-based residues. Polyoxyalkyleneamines may be obtained from, e.g., BASF, Mt.Olive, N.J. and Huntsman Chemical, Salt Lake City, Utah. Commercially available polyoxyalkyleneamines and selected properties are given in TABLE D (TABLE Dxe2x80x94TYPICAL POLYOXYALKYLENEAMINES AND THEIR PROPERTIES). In TABLE D, both the XTJ and JEFFAMINE(trademark) tradenames are used by Huntsman Chemical.
The diamine may be a polyether diamine, also referred to herein as a PAO (for polyalkyleneoxy) diamine. Polyetherdiamines may be obtained from Huntsman Chemical. A suitable polyether diamine is a poly(propyleneoxy)diamine such as JEFFAMINE(copyright) D-400. Another suitable diamine is a poly(ethyleneoxy)-co-propyleneoxy) diamine such as HUNTSMAN XTJ-500. Yet another suitable diamine is JEFFAMINE(copyright) EDR-148, which is also known as triethyleneglycoldiamine, having CAS Registry No. 929-59-9 and the chemical structure H2Nxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2CH2xe2x80x94NH2. In one embodiment, the polyetherdiamine has the structure NH2CH(CH3)CH2Oxe2x80x94(CH2CHRxe2x80x2O)xxe2x80x94CH2CH(CH3)NH2, where R and Rxe2x80x2 are methyl or H.
Use of a significant level of both polyether diamine and polyether monoamine provides resins having the ability to form clear solutions and/or clear gels in a wide range of polar solvents including propylene glycol, ethanol, polypropylene glycol and polyethylene glycol and their monoalkyl ethers. At high weight percentage use levels of terminator (i.e., hydrocarbon-terminated polyether), the resins are extremely soft. As the total level of polyether in the polyamide block decreases, the resin gains the feel and flexibility of a polyamide prepared from ethylene diamine and dimer acid, thus retaining some softness even at low levels of polyether. Some of these resins may dissolve in ethanol, but most demonstrated good solubility in propanol, however gelling behavior was infrequent. In general, propylene glycol is a preferred solvent to prepare gels from solvent and resins of the invention (i.e., resins prepared from polyether diamine and polyether monoamine). In general, formation of dimer-acid based polyamides, even those including a significant level of both polyether diamine and polyether monoamine among the reactants leads to a resin that it not particularly compatible with glycerol.
When a polyether diamine and polyether monoamine-derived resin is dissolved in a polar solvent, and then this solution is diluted with water, it is typically observed that the solution remains homogeneous, i.e., the resin does not precipitate. Frequently, upon dilution with water, the resin/polar solvent/water mixture takes on a bluish cast, indicating the presence of a microemulsion form.
In preparing the resins of the present invention, it may be noted that the diamine may be a mixture of hydrocarbon diamine and polyether diamine. In addition, it is generally observed that increasing the level of termination, i.e., increasing the relative amount of monoreactive hydrocarbon-terminated polyether, tends to provide a resin with a relatively lower softening point and melt viscosity. The use of hexamethylene diamine (HMDA), in lieu of some or all of ethylene diamine (EDA), tends to lower the softening point of the resin. The inclusion of co-diacid, i.e., diacid other than dimer acid, e.g., sebacic acid, in the reaction mixture tends to raise the softening point of the resulting resin. The polyether monoamine should not contain any hydroxyl groups. The inclusion of hydroxyl groups is detrimental to the gelling ability of the resin made from the monoamine. Accordingly, hydroxyl terminated polyethers are not included within the polyether monoamine reactants of the present invention.
Some of the inventive resins, particularly those prepared from polyether diamines and polyether hydrocarbon-terminated monoamines, have the unusual ability to form microemulsions in mixtures of water and a polar solvent. These blends are clear and homogeneous but have a distinct blue cast and can be either immobile gels or fluid liquids, depending on the concentration of the resin and the polar solvent. They can be diluted with water without formation of a precipitate. Block copolymers of the present invention that form such microemulsions may be particularly useful as corrosion inhibitors in aqueous systems.
As described herein, diamines, dicarboxylic acids, and hydrocarbon-terminated polyethers having a reactive group W selected from hydroxyl, amine and carboxyl are preferred starting materials to form the triblock copolymers of the invention. These starting materials are preferably reacted together with a stoichiometry, and under reaction conditions, such that the acid number of the resulting block copolymer is less than 25, preferably less than 15, and more preferably less than 10, while the amine number is preferably less than 10, more preferably less than 5, and still more preferably less than 1. The softening point of the block copolymer is preferably greater than room temperature, more preferably is about 50xc2x0 C. to about 150xc2x0 C., and still more preferably is about 75xc2x0 C. to about 125xc2x0 C.
It is important to control the stoichiometry of the reactants in order to prepare a block copolymer according to the invention. The following discussion regarding reactant stoichiometry uses the terms xe2x80x9cequivalent(s)xe2x80x9d and xe2x80x9cequivalent percentxe2x80x9d, where these terms are intended to have their standard meanings as employed in the art. However, for additional clarity, it is noted that equivalents refer to the number of reactive groups present in a molar quantity of a molecule, such that a mole of a dicarboxylic acid (e.g., sebacic acid) has two equivalents of carboxylic acid, while a mole of monoamine has one equivalent of amine. Furthermore, it is emphasized that in preparing a triblock copolymer of the invention, the diacid has only two reactive groups (both carboxylic acids, although dimer acid may contain a small amount of tricarboxylic acid), the diamine has only two reactive groups (both primary amines) and the hydrocarbon terminated polyether reactant has a single reactive group selected from amine, hydroxyl and carboxyl. Furthermore, these are preferably, although not necessarily, the only reactive materials present in the reaction mixture.
When co-diacid is employed to prepare a block copolymer, the co-diacid preferably contributes no more than about 50% of the equivalents of carboxylic acid present in the reaction mixture. Stated another way, the co-diacid contributes from 0-50 equivalent percent of the acid equivalents in the reaction mixture. Preferably, the co-diacid contributes 0-30 equivalent percent, and more preferably contributes 0-10 equivalent percent of the acid equivalents in the reaction mixture.
The stoichiometry of the reactants will have a significant impact on the composition of the block copolymer. For example, triblock copolymers made with increasing amounts of polyether will tend to have lower (number and weight) average molecular weights. On the other hand, as less polyether is used, the average molecular weight of the molecules that comprise the block copolymer will increase. In general, increasing the average molecular weight of the copolymer will tend to increase the melting point and melt viscosity of the copolymer. When a high melting point copolymer is combined with a solvent to thereby form a gel, the gel will tend to have a firmer consistency than does a gel formed from a copolymer with a low melting point.
In order to prepare a block copolymer of the present invention, the above-described reactants (diacid, diamine and polyether, or reactive equivalents thereof) may be combined in any order. In one embodiment of the invention, the reactants are simply mixed together and heated for a time and at a temperature sufficient to achieve essentially complete reaction, to thereby form the block copolymer. In another embodiment, the diacid and diamine are reacted together, followed by addition of the monoreactive polyether. During formation of the block copolymer, the diacid and diamine compounds will alternate to form what may be termed an alternating copolymer, i.e., the polyamide block of the block copolymer is an alternating copolymer of diacid and diamine. The terms xe2x80x9ccomplete reactionxe2x80x9d and xe2x80x9creaction equilibriumxe2x80x9d as used herein have essentially the same meaning, which is that further heating of the product does not result in any appreciable change in the acid or amine numbers of the copolymer.
Thus, the block copolymer may be formed in a one-step procedure, wherein all of the diacid (including co-diacid), diamine and polyether are combined and then heated to about 180-250xc2x0 C. for a few hours, typically 2-8 hours. When lower temperatures are used, a longer reaction time is typically needed to achieve complete reaction. When the reaction temperature is too high, the reactants and/or products may undergo undesirable thermally-induced decomposition. Typically, the reactants must be exposed to a temperature in excess of 100xc2x0 C. in order to drive off the water formed by the condensation of the reactants. Since one or more of the reactants may be a solid at room temperature, it may be convenient to combine each of the ingredients at a slightly elevated temperature, and then form a homogeneous mixture prior to heating the reaction mixture to a temperature sufficient to cause reaction between the diacid, diamine and polyether. Alternatively, although less preferably, two of the reactants may be combined and reacted together, and then the third reactant is added followed by further heating until the desired product is obtained. Reaction progress may be conveniently monitored by periodically measuring the acid and/or amine number of the product mixture.
As one example, dimer acid may be reacted with diamine so as to form polyamide, and then this intermediate polyamide may be reacted with polyether to form a hydrocarbon terminated polyether-polyamide-polyether block copolymer. Because the components of the block copolymer are preferably in reaction equilibrium (due to transamidation and/or transesterifiction reactions), the order in which the reactants are combined typically does not impact on the properties of the product copolymer.
Any catalyst that may accelerate amide and/or ester formation between carboxyl, amine and/or hydroxyl groups may be present in the reaction mixture described above. Thus, mineral acid such as phosphoric acid, or tin compounds such as dibutyltin oxide, may be present during the reaction. In addition, it is preferred to remove water from the reaction mixture as it is formed upon amide and, optionally, ester formation. This is preferably accomplished by maintaining a vacuum on the reacting mixture, or by passing a stream of an inert gas (e.g., nitrogen) across the top of the reaction mixture.
The block copolymers of the invention may be used to thicken and/or gel a solvent (where the term xe2x80x9ca solventxe2x80x9d includes a mixture of solvents). As used herein, the term solvent includes any substance which is a liquid at a temperature between 10-60xc2x0 C., and which forms a gel upon being combined with a block copolymer of the present invention. As used herein, the term solvent will be used to encompass oils and other fluids that may be gelled by the block copolymer of the invention, and is not otherwise limited.
The combination of block copolymer and solvent has a gel-like consistency. In general, materials that have a gel-like character will maintain their shape when undisturbed but flow upon being rubbed. Gels prepared with block copolymers of the present invention may be anywhere from soft to hard, where a xe2x80x9chardxe2x80x9d gel has a rigid structure and is very resistant to deformation, while a xe2x80x9csoftxe2x80x9d gel exhibits some, but not too much, resistance to deformation. An illustration of xe2x80x9csoftxe2x80x9d gel may be seen in the preparation of Jell-O(copyright) dessert, which is a well known food product from Kraft Foods Inc. (division of Philip Morris Companies Inc., Northfield, Ill.). When prepared according to the package instructions, Jell-O(copyright) dessert is mixed with water to form a relatively soft gel.
The solvent is a liquid at room temperature or slightly above room temperature. A preferred solvent is a polar solvent, where exemplary polar solvents include lower alcohols (e.g., methanol, ethanol, propanol, butanol), glycols, ethers, glycol ethers (i.e., polyalkyleneglycol ethers), and polyols. The polar solvent may be a mixture of solvents. Exemplary polar solvents are described in TABLE E (TABLE Exe2x80x94POLAR SOLVENTS CONTAINING HYDROXYL AND/OR ETHER FUNCTIONALITIES). DOWANOL(trademark) E-200 and E-300 are two exemplary polyethylene glycols from the DOWANOL(trademark) family of glycol ethers from Dow (Midland, Mich.; www.dow.com) while DESMOPHEN(trademark) 550 U and 1600 U are polyether polyols from the DESMOPHEN(trademark) family of products from Bayer Corporation (Pittsburgh, Pa.; www.bayer.com).
Preferably, the solvent is a polar liquid as described above, and more preferably the solvent is a liquid that contains ether and/or hydroxyl groups. The liquid may contain more than one component, e.g., ether as well as hydroxyl-containing material. In the mixture, the gellant (block copolymer) typically contributes 10-95%, and the solvent typically contributes 5-90%, of the combined weight of the gellant and the solvent. Preferably, the gellant is combined with the solvent such that the weight percent of gellant in the gellant+solvent mixture is about 5-50%, and preferably is about 10-45%. Such gels may be transparent, translucent or opaque, depending on the precise identities of the gellant and solvent, as well as the concentration of gellant in the mixture.
In order to prepare a gel from a solvent and block copolymer, the two components are mixed together and heated until homogeneous. A temperature within the range of about 80-150xc2x0 C. is typically sufficient to allow the block copolymer to completely dissolve in the solvent. A lower temperature may be used if a solution can be prepared at the lower temperature. Upon cooling, the mixture forms the gelled composition of the invention. Optional components may be added to the molten composition, and are dispersed and/or dissolved to provide a homogeneous composition prior to cooling of the molten composition.
In another embodiment, the block copolymer-containing gels of the present invention may be formulated such that they are transparent. There are various degrees of transparency, ranging from xe2x80x9ccrystalxe2x80x9d clear to hazy, which may be achieved with gels of the invention. In order to provide some measure of the absolute transparency of a gel, the following test has been devised. A white light is shined through a gel sample of a given thickness at room temperature, and the diffuse transmittance and the total transmittance of the light are determined. The percent haze for a sample is determined by the equation: %haze=(diffuse transmittance/total transmittance)xc3x97100. Samples are prepared by melting the gel (or product made therefrom) and pouring the melt into 50 mm diameter molds. The samples may be prepared at two thicknesses, e.g., 5.5xc2x10.4 mm and 2.3xc2x10.2 mm.
Clarity measurements are made on a Hunter Lab Ultrascan Sphere Spectrocolorimeter using the following settings: specular included, UV off, large area of view, illuminate D65, and observer 10xc2x0. Using this protocol with a 2.3 mm thickness sample, an ATPA gel of the present invention may have a %haze value of less than 75, while paraffin wax has a %haze value of over 90. The %haze value for a gel of the present invention can be increased if desired, by appropriate selection of solvent and gellant. Thus, the present invention provides gels (and articles made therefrom) having a transparency (measured by %haze) of less than 75, preferably less than 50, more preferably less than 25, still more preferably less than 10, and yet still more preferably of 5 or less.
In one embodiment, the gels containing block copolymer of the present invention are also stable, in that they do not display syneresis. As defined in the McGraw-Hill Dictionary of Scientific and Technical Terms (3rd Edition), syneresis is the spontaneous separation of a liquid from a gel or colloidal suspension due to contraction of the gel. Typically, syneresis is observed as the separation of liquid from a gel, and is sometimes referred to as xe2x80x9cbleedingxe2x80x9d, in that wetness is seen along the surfaces of a gel that displays syneresis. From a commercial point of view, syneresis is typically an undesirable property, and the gels of the present invention desirably, and surprisingly do not exhibit syneresis. In one embodiment, the gels of the invention, and articles prepared therefrom, may be stable in the sense that they do not exhibit syneresis. Thus, they do not have an oily feeling when handled.
A gel formed from a block copolymer and the present invention may be used to prepare an antiperspirant or deodorant. The antiperspirant may also contain one or more of aluminum chlorohydrate, aluminum-zirconium tetrachlorohydrate, aluminum-zirconium polychlorohydrate complexed with glycine, and aluminum-zirconium complexed with any of trichlorohydrate, octachlorohydrate, and sesquichlorohydrate. The gels, and the formulated antiperspirant, are preferably transparent.
The block copolymer-containing gels of the invention may be (although need not be) essentially transparent. When transparent, the gels may be combined with colorants (as well as other ingredients) to form lipstick or other cosmetic products, without the gel interfering with or tainting the appearance of the colorant. The gels of the present invention may be combined with aluminum zirconium salts, as well as other ingredients, to form colorless underarm deodorant/antiperspirant, which is currently quite popular. The gels of the invention are also useful in other personal care products, e.g., cosmetics such as eye make-up, lipstick, foundation make-up, costume make-up, as well as baby oil, make-up removers, bath oil, skin moisturizers, sun care products, lip balm, waterless hand cleaner, medicated ointments, ethnic hair care products, perfume, cologne, oral care bases (e.g., for toothpaste) and suppositories.
In addition, the gels of the present invention may be used in household products such as air fresheners, decorative table-top food warmers (i.e., they may be burned slowly to heat, e.g, an overhead chafing dish), automobile wax/polish, candles, furniture polish, metal cleaners/polishes, household cleaners, paint strippers and insecticide carriers.
Formulations to prepare such materials are well known in the art. For example, U.S. Pat. Nos. 3,615,289 and 3,645,705 describe the formulation of candles. U.S. Pat. Nos. 3,148,125 and 5,538,718 describe the formulation of lipstick and other cosmetic sticks. U.S. Pat. Nos. 4,275,054, 4,937,069, 5,069,897, 5,102,656 and 5,500,209 each describe the formulation of deodorant and/or antiperspirant.
The block copolymer of the invention may be incorporated into commercial products such as those listed above, as well as cable filling compounds, urethane/alkyl paint additives, and soaps/surfactants. These products may be prepared by blending the block copolymer with the other components of the product. In these commercial products, the block copolymer will typically be present at a concentration of about 1% to about 50% of the composition, based on the total weight of the composition. It is a routine matter to optimize the amount of block copolymer in a composition, and indeed the amount will vary depending on the actual product and the desired consistency of the product. In general, as more block copolymer is used in a formulation, the product will display a more pronounced gel character, and will form a more rigid, or hard, gel.